DE1903536A1 - Process to avoid agglomeration - Google Patents

Description

DR.w. Schalk ... · Dipl.-Ing. p. Wirth dipl.-ing. c. Dannenberg DR-V-SCHMIED-KOWARZIK, - D'R.P.WEINHOLD

6 FRANKFURT AM MAIN,

CR. ESCHENHEIMER STR. 39

Case: 1158

January 13, 1969

Wd / B

Mo och Domsjö Aktiebolag Örnsköldsvik / SWEDEN

"Process to avoid agglomeration"

The present invention relates to a method for preventing agglomeration of primary resin particles in the fiber suspension, in which a new type of resin regulating agent is used, with which the resin particles are well fixed in the fibers and / or the resin substances to be made soluble.

An agglomeration of primary resin particles in fiber * Spensions can cause sticky (harmful) resin build-ups result. These agglomerations are either on the cellulose-loose substance in the form of resin stains or in the Devices for bleaching and papermaking, e.g. in Micrometers, towers, dutch housings, mills, wires, sieves, filters, etc., are deposited. There were different ones Proposed methods of combating these difficulties with the aid of various additives. These proposals are based on various modes of operation, but all known types of resin control agents that are used in this context, have certain, very serious cons.

In recent proposals, non-ionic! • drug dispersants, e.g. ;; ethylene oxide to fatty alcohols were used.

-: - - -; 009842/1731

SAD

The behavior of such a surface-active detergent is such that its lipophilic components turn towards the lipophilic resin particles, while the hydrophilic component is directed towards the water phase and is hydrated. In this way, the additive creates a permanent dispersion of the primary resin particles, which are then removed from the system through a partially open backwater system. However, one of the disadvantages associated with such resin dispersants is that they tend to be very large; To form foam. This prevents as much von'dem nonionic Dispergierungsmitteü can be added to / as W is desirable. The usability of such dispersants in the paper industry, where "largely closed or condensation water systems are used, is very limited because of the technical problems caused by difficulties due to foaming, binding difficulties and precipitation of the resin in the overloaded because of the accumulation of the slack water system occur. Furthermore, easily arise difficulties währerd the early days, as old resin agglomerations tend to dissolve as soon as surfactants Harzdispergierungs- _ medium are added.

Another type of resin dispersant is cationic (positively charged) surfactants or water-soluble salts of primary, secondary or tertiary amines in the form of fatty amines with a carbon chain usually about Cj ^ -CjQ * where the mode of action of the cationic additive is interpreted in this way that the anionic resin is deposited in finely divided form on the solid > ■ . In this way build-ups of the free resin are avoided. A disadvantage of such resin dispersants is that the primary, tertiary amines that are mainly used are practically non-cationic at a pH greater than 6-7, which makes the usefulness of such dispersants strongly pH-dependent. The effect is even.

009842/1731

strongly dependent on the dosage "because a small overdose" has a very negative impact on the result. This effect is based on the fact that the resin particles are positively charged by excess cationic substances, so that these particles are precipitated in the form of sticky resin agglomerates. When using cationic quaternary compounds of surface-active substances, their cationic activity is retained at pH values greater than 6 - 7, although there is a great tendency to foam formation, which limits the dosage and binding difficulties and an unstable initial period, as described above was caused. Another disadvantage of cationic surface-active substances is that the brightness of the fibers is not improved, but rather is impaired, since the resin is not washed away but rather sticks to the fiber. In addition, these types of additives cannot be used for viscous wood pulps. * ¹ "Other types of resin control agents include inorganic mineral substances, e.g. talc or asbestos fibers. When these resin control agents are used, the small, sticky primary resin particles are coated or dusted with the added substances, see above that agglomeration is avoided. It is believed that the asbestos fibers act because of their positive charge, whereby the anionic resin is deposited on the fibers in finely divided form. The disadvantages associated with these types of products are that the required high amount Dose (0.5-2 # of the weight of the cellulose) make the process very costly, although the additive price per kilo is low, and for a good result the additive must be added at an early stage of the process, despite the retention ability the Substmz considerable, from about 80 i-> a to about 50 <3 or lower.

009842/173 1
BAO

Another disadvantage is that the protective layer eventually becomes during the grinding process due to the shear forces that occur partially exfoliates, exposing and agglomerating the resin particles. The obtained with asbestos Results are poor at high pH values, "because the asbestos particles are recharged." After all, the metering of inorganic minerals often causes difficult problems.

With the present invention a new method for Solution of the mentioned problems created by an essentially new resin regulating agent is used, which is characterized by a combination of the following properties

is: .. ■■ ·. '.

1. Water solubility

2. positive charge independent of the pH value

3. no surface activity

The latter characteristic is understood to mean a non-surface activity according to conventional norms', "i.e. the Surface tension measured at 20 G according to De Notly in one aqueous solution containing 5-500 mg / l of the substance exceeds 50 dynes / cm.

The structure of the non-surface-active quaternary ammonium compounds, the 'according to the invention as a resin control agent can be used by the following general Formula to be represented!

R,

09842/1731

in which at least one, at most all four of the radicals' R ₁ (Rp Rz and R. the radicals G Hp _{n +} -I and / or one or more of the radicals (G ₂ H ₄ O) _1n H, (OXO) H and ( C ₄ H ₈ O) JI, where X _{= HSO 4} , GH ₅ SO ₄ , G ₂ H ₅ SO ₄ , Cl or Br, η = 1-4, m = 0-10, ρ = 0-5 and q = 0-2 is.

Quaternary triethanolamines, which are particularly suitable according to the invention are mainly those of the following formula:

-β +

HOG ₂ H ₄ N CH ₅ SO ₄ T * f / * \ <* Ί TT "^^^
i ~ L Jl τι j έ 4> GH, TT / ^ Srt TT ^^

The triethanolamine can be prepared in a conventional manner by adding ethylene oxide to ammonium. Although the manufactured technical product, which is mixtures of mono-, Contains diethanolamines and triethanolamines together with higher alkoxylated derivatives as starting material for the following Quaternization method can be used, it is common subjecting the product obtained to a distillation process, the triethanolamine fraction in the form of a product, with a purity of. about $ 98-99 is removed. The quaternary resin non-surfactant control agent can be prepared from the obtained triethanolamine by it is' quaternized with dimethyl sulfate in a known manner.

The addition of quaternized triethanolamine or similar compounds as a resin regulating agent has the effect that the negatively charged resin particles adhere to the negatively charged cellulose fiber because of their positive charge, so that agglomerations are avoided. This corresponds to the behavior * _:

0098 42/1731 *

of cationic substances "" The added substance, but also the enveloped _f Harzte.ilchen and its surface is transformed state from a lipophilic state to a hydrophilic, thereby obtaining the solubility conditions according to the behavior of the surface active nonionic Harzdispergierungsmittel. In this way and due to the solubility of the product in water, the sensitivity for overdose is _f, the secondary or primary with the use of cationic surface-active substances or water-soluble salts of the _"9 tertiary Pettamine is connected prevented. _9, however, the most important advantage is that the product Because of its non-surface activity there is no cause for difficulties due to foaming, gloss and resin precipitation in "overloaded" systems and there is also no unstable application period. * · * Furthermore, the product can be added undiluted in concentrated form. It is not dependent on pH - Fluctuations, nor difficulties arise during grinding, since the action ^: (binding) of the product on the resin takes place in molecular dimensions.Finally, it was found that only small additions are necessary in order to achieve the desired effect.

Examples of suitable starting materials for the inven tion according to the invention Quaternization and production of resin regulators are mono-, di- or trimethylamines ■ Mono -, - Pi- or triethanolamine, mono-, pi- or tripropanolamine, mono-, Di- or tributanolamine in the form of pure substances or technical mixtures. Furthermore, ethylene oxide, propylene oxide and / or.-butylene oxide to which alkanolamines are added in the product prior to quaternization. Is dimethyl sulfate particularly good for use as a Quaternizing agent suitable. Examples of other quaternizing agents are mainly ethyl sulfate, methyl or. Ethyl chloride and methyl or ethyl bromide.

271731 BAOORIÖINAL

i- '- i:. ■ '·.': 1303536

It was found that the resin control agent too at any time during the manufacture of the wood pulp and / or the paper are added, the Dosage up to $ 1, based on the weight of the cellulose, can be. The following examples explain the application and mode of action of the product in more detail:

Example 1

1MoI 98 # triethanolamine, was quaternisfert at 25-3O ⁰ C with 1 mol of dimethyl sulphate. The product obtained was a yellowish liquid which was slightly viscous at room temperature. The surface activity of the product was determined by the surface tension thereof was measured in aqueous solution at 20 ⁰ C after de Notly at different concentrations of the quaternary Triethanolamine. Was used as comparison substance at the same concentration of C was _1g -C ₁₈ fatty alcohol at the 18 moles of ethylene oxide per mole of fatty alcohol are added, the results can -Uses the fol _fa * of tables to be removed.

Concentration mg / l
aqueous solution Surface tension
dyn / cm 72 Quaternary fatty alcohol ^ ethylene-
Triethanolamine oxide adduct 46 0 72 42 5 72 40 20th 71 less than40 200 67 "« 40 500 59 1000 51

0098A2 / 1.73.1
BATH ORIGINAL

A comparison shows that the quaternary triethanol,; amine derivative not surface-active according to conventional pre-f Positions is because the surface tension reducing effect is quite low. ν

B e i s .ρ i e 1 2

A comparison foam test was carried out with the same products, as indicated in Example 1 carried out. Ig of the product was dissolved in 1000 ml of distilled water. 300 ml of the aqueous Solution was placed in a graduated mixing cylinder (500 ml), which was brought into a rotating device, which was the mixing cylinder at a speed of 1 revolution per 1.5 sec. turned. After 15 seconds of rotation, the height of the Read the foam in the cylinder and read it in ml above the surface of the liquid registered. The result can be seen in the following table:

Time after completion Remaining foam - fatty alcohol-ethylene-
oxide adduct the rotation of the Zy
linders. Quaternary
Iriethanolamine 90 ml ' 0 sec 10 ml 90 » 20 » O " 70. " 300 " 0 » '

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A comparison shows that with the non-surface-active cationic ^: triethanolamine derivative only slight foam formation was obtained initially, the foam also collapsing quickly. With the surface-active fatty alcohol derivative, on the other hand, a relatively large amount of solid foam is obtained.

Example 3

Tests were carried out to measure the amount of the harmful resin on a copper surface according to Ch-. Gustafsson.! This method, which is well known in the cellulose and paper industry .: is _% is used to determine the amount of resin, of the so-called "harmful resin" that is deposited on a rotating copper stirrer,:. ¹ Ss is for example used in detail in "Das Papier" ·, 10th paper 13 / H - page -266 (1954) « ^; The result can be taken from the following table: '

Addition of the weight of the wood pulp mass in fo .

mg of harmful resin per 200 g of unbleached: SuIfite wood pulp. '-.- · -:

o '' io '■ _ "■■;■" ■ ' ■ ^:

0.05 ^ .Quaternary triethanol- amih after "Example 1

0.10 $ \ y 0.20 io - ,> .. '""

0.05 1 " fatty alcohol-ethylene oxide adduct according to Example-1

0.10 f "" ■ ^ir ; "

0.20 i

0.10 i> talc 0.20 io talc

150

124 -; ■■ - .. ■ ''.-.- "

^: 70 ^:

69 r ■

115

65 (very uncomfortable difficulties with foaming and gluing)

53] ... "
152
280

"0 0 as4--2 ^ - '1" 7.3- "t

- ίο - ·

-p. ,. '■. · / Substance

The experiment zexgt that the inventive large effective?

wedge / in the resin regulation, without the hassle
Foaming and sizing as with that
non-ionic product occur. ; ',.:;

In this experiment, triethanolamine, which was produced according to Example Ί-- was quaterriated with dimethyl sulfate. For loading ■
The mood of the effectiveness of the resin regulating agent was - ■■: ■ -. ·;.,; the amount of harmful resin is determined by flotation. . ., ..; j The flotation device consisted of a Hallimond tube ,. ; ■, the lower part of which was provided with a glass filter. 1.20 igl / _:. ; Min. Nitrogen gas was through the overlying Sasersu? · ??; ^ -; Board (100 ml, 1 fa birch wood pulp) at a liquid ^{temperature of 20 0} C blown. The floated resin was; «· _; gev / ogen. The result can be seen in the following table. * - ?;

Focus on. quaternary em,
Triethanolamine, ppm based
on the weight of the 'fiber suspension - · .. "■■, · ■■ -' ■ : - '·. · - ■ .- '

-ίο.; 'i. "'~'^{vr; f} '"""'"■ ^. '5ö
'50 "■" ^: ' ^: . ; ^: ■ '■ "■" .- ■ - ■' ■ 22;

As can be seen from the table, the addition of -des- ^
quaternary non-surfactant triethanoiamine derivative; the .
Formation of harmful resins both with one.] Acid as: also ..
an alkaline; pH value successful. prevented. - ^ ■ ".- ·". . "- ;;;

B e i 8 ρ i el "5,

Using the same device and application The same procedure as in Example 4 became 50 ppm Of triethanolamine quaternized with diethyl sulfate to 100 ml of 0.5 # suspension of spruce pulp (fir pulp) given, 10 moles of ethylene oxide per mole of triethanolamine were the triethanolamine before the quaternization process has been added. At test conditions of 20 C and a .pH value of 5 was the amount of harmful Resin from 30 mg before the blank tests (without resin control agent) to 17 mg in the presence of the resin control agent reduced. At a pH value of 8, but in other respects the same conditions, the proportion of harmful resin reduced from 11 mg to 5 mg.

Example 6

Using the same apparatus and procedure as in Example 4, 50 ppm of a resin control agent prepared by adding 2 moles of propylene oxide and immediately thereafter 4 moles of ethylene oxide to 1 mole of butylamine was added to 100 ml of a 1 $ suspension of Birch pulp was added, whereupon the product obtained was quaternized in a known manner by treatment with 1 mol of dimethyl sulfate. Under test conditions of 20 ^° C. and a pH of 5, the proportion of floating harmful resin was reduced from 46 mg in the blank test to 26 mg in the presence of the resin regulating agent.

Be is pie I 7

Offset paper, was made from a wood pulp mixture of * 75% bleached sulfate pulp and 25 # bleached sulfite pulp. This pulp mixture were added 3 # alum, 1 $ resin adhesive, 5 $ beaten or ground starch and 0.1 fi quaternized, prepared according to Example 1 Triäthanol--

amine

00 9 84 2/1731. Hi

Unmixed. The quantities dispensed refer to the Weight of the paper »The pH of the suspension was 4.5.

o The weight of the paper produced was 80 g / cm. The sizing effect was characterized by determinations of the Cobb-Dennison and surface sizing values. The values obtained with blind tests were 25-6 and 14 .. These values were not influenced by the addition of quaternary triethanolamine, which proves that the sizing was not adversely affected,

Ά e i s · ρ ■ i e 1 8

/in
On an industrial scale experiment, based on the weight of the wood pulp, 0.2 $ of a quaternized triethanolamine prepared according to Example 1 was added to the fiber suspension instead of the 1.5 # talc powder usually used. Of the. The precipitate obtained on the wire was reduced by 50% compared to that obtained when using talc powder. No foaming or gluing problems could be determined «

00 98 4 2

Claims (8)

P a t e nt a η g. ρτ-ü'c h e / ■ ". '" 1. Process for regulating resin in cellulose and paper manufacture, characterized in that the resin regulating agent a quaternary amine non-surfactant compound represented by the following general formula in the system is used: . X " in which at least one, at most all four of the residues Rp, R, and R. the radicals ^ n ^ / or one or comprise several of the radicals (C ₂ H.0) _m H, (C ₅ HgO) H and (CVHjQ) -H and X = HSO., CH _{5 SO 1} , O 2 H ₅ SO, Cl or Br, η = 1-4, m = 0-1Ό, ρ = 0-5 and q = 0-2, wherein the resin control agent can be introduced after cooking at any time during the wood pulp and / or paper production. cv 2. A method for regulating resin according to claim 1, characterized in that a resin regulating agent is used with Dimethyl sulfate quaternized triethanolamine is used. 3. A method for regulating resin according to claim 1, characterized in that a resin regulating agent The addition product of about 3-10 moles of ethylene oxide with triethanolamine is quaternized with dimethyl sulfate has been used. 009842/1731 BADORfGlNAt ... 4. A method for regulating resin according to claim 3, characterized in that that the resin regulating agent used is one which, by addition, has about 3-9 moles of propylene oxide after the ethylene oxide addition, or before the ^ quaternization stage and subsequent quaternization with dimethyl sulfate. 5. The method for regulating resin according to claim 1, characterized in that such a resin regulating agent is used by the simultaneous addition of a mixture of about 50-90 wt .- $ ethylene oxide and about 10-50 G-ew -.- fi Proßv.lenoxyd on propylenamine and subsequent quaternization with dimethyl sulfate. 6. The method for regulating resin according to claim 1, characterized in that such a resin regulating agent is used, the addition of about 3-30 moles of ethylene oxide to 1 mole of ammonium, subsequent addition of about Mole 3-D butylene oxide, and subsequent quaternization with dimethyl sulfate has been produced. 7. The method according to claim 1-6, characterized in that the quaternizing agent in an amount of about 0.2-1 mole per mole of tertiary amine has been used. , 8. The method according to claim 1-7, characterized in that as Quaternizing agent diethyl sulfate or methyl chloride has been used. The patent attorney 09 84 2/17 3 1
BATH ORIGINAL